Time-dependent and coupled-perturbed DFT and HF investigations on the absorption spectrum and non-linear optical properties of push–pull M(II)–porphyrin complexes (M=Zn, Cu, Ni)

Synthesis, EPR and DFT calculations of rare Ag(II)porphyrins and the crystal structure of [Zn(II)tetrakis(4-bromo-2-thiophene)porphyrin]

“…The model system Ag(II)porphyrin 6 was investigated by DFT 4 (calculations on similar large open shell porphyrins have recently been reported [48]) and we found spin populations +0.44 for Ag and +0.09-+0.14 for N, thus accounting for 91% of the positive spin density in the molecule, the remaining density being evenly spread out over the porphyrin system. No significant negative spin density was found, and our conclusion is that some significant delocaliza- 2 The natural abundance of different isotopes of Br, Zn and Ag makes unambiguous assignments possible even on a low-resolution instrument, and patterns matching the calculated isotopic pattern were found for all the compounds.…”

Theoretical study of structure and non-linear optical properties of Zn(II) porphyrin adsorbed on carbon nanotubes

“…There have been several theoretical studies in the literature on metal porphyrins, mainly molecules having acceptor and donor groups of electrons [19,23]. Tillekaratme et al [23], for example, used the semi-empirical AM1 method to obtain the starting molecules of protonated porphyrins, which were re-optimized at the ab initio HF/3-21G level, for further studies of their NLO properties.…”

“…Tillekaratme et al [23], for example, used the semi-empirical AM1 method to obtain the starting molecules of protonated porphyrins, which were re-optimized at the ab initio HF/3-21G level, for further studies of their NLO properties. Density functional theory (DFT) calculations were also employed [19,24] using the functional BLYP and B3LYP in conjunction with the minimal basis set. For the theoretical calculation of the NLO properties of organic chromophores, the literature shows semiempirical calculations such as CNDO/S, INDO/S [12], ZINDO, MNDO, AM1, PM3 [25] and PM6 [12], in addition to various ab initio calculations, at HF, using basis sets, STO-3G, 3-21G and 6-31G [23], MP2 [12] and DFT levels with the functional SVWN, BLYP and B3LYP [12,26], among others.…”

“…The results obtained showed that the values of b increased significantly ($70%) when (E)-stilbene was modified by electron donor groups. In the literature [14][15][16][17][18][19] there are some studies involving hybrid compounds of tetraazomacrocycle molecules and nanotubes, with particular interest in their electronic and optical properties. Among this group of molecules, those belonging to the family of porphyrins should be highlighted, in which a large number of organic pconjugated molecules have been investigated for their suitability to serve as molecular components in hypothetical NLO materials [20].…”

Synthesis and characterization of tetraarylporphyrins in the presence of nano-TiCl4·SiO2

“…7 Also, they are used for optical applications in e.g. data storage, 8 nonlinear optics, 9,10 electrochromism, 11 etc., which are just few of the many areas that have inspired the synthesis of porphyrin-based compounds. Porphyrins are used as catalysts, [12][13][14] photosensitizers, 15 nonlinear optical materials, 16 liquid crystals, 17,18 in photovoltaic cells, 19 lightharvesting complexes, 20 as well as in photodynamic therapy of cancer.…”